JP2012203355A - Photosensitive composition, photosensitive laminate, permanent pattern forming method, and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which is excellent in all of insulation performance, thermal shock resistance, and resolution; and a photosensitive laminate, a permanent pattern forming method, and a printed circuit board using the photosensitive composition.SOLUTION: A photosensitive composition contains an acid-modified ethylenically unsaturated group-containing urethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, and a photopolymerization initiator.

Description

  The present invention relates to a photosensitive composition, a photosensitive laminate, a method for forming a permanent pattern, and a printed board.

  Conventionally, when forming a permanent pattern such as a solder resist, a liquid resist or a photosensitive film having a photosensitive layer formed by applying a photosensitive composition on a support and drying it has been used. As a method for forming a permanent pattern such as a solder resist, for example, a laminate is formed by laminating a photosensitive layer using a liquid resist or a photosensitive film on a substrate such as a copper-clad laminate on which a permanent pattern is formed. A method of forming a permanent pattern by exposing the photosensitive layer, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like is known.

  In the photosensitive composition that can be used for the solder resist, improving insulation, thermal shock resistance, and resolution is one of important issues, and various studies have been made.

For example, photopolymerizable epoxy (meth) acrylate resin, photopolymerizable urethane (meth) acrylate resin, and photopolymerization having one terminal (meth) acrylate group having a molecular weight of 250 to 650 and no carboxyl group. A photocurable solder resist ink containing a functional compound has been proposed (see Patent Document 1).
A photosensitive resin composition comprising (A) an acrylic resin, (B) a polyurethane resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a phosphorus-containing compound. The (B) polyurethane resin is a photosensitive resin that is a reaction product of an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group. A composition has been proposed (see Patent Document 2).

  However, these proposed technologies contain an ethylenically unsaturated group-containing urethane resin, and thus have a problem that the thermal shock resistance is excellent, but the insulation and resolution are not sufficient.

  Accordingly, there is a demand for providing a photosensitive composition excellent in all of insulation, thermal shock resistance, and resolution, and a photosensitive laminate, a method for forming a permanent pattern, and a printed board using the photosensitive composition. The current situation is.

JP-A-61-103968 JP 2010-282001 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a photosensitive composition excellent in all of insulation, thermal shock resistance, and resolution, and a photosensitive laminate, a permanent pattern forming method using the photosensitive composition, and a printed board. With the goal.

Means for solving the problems are as follows. That is,
<1> A photosensitive composition comprising an acid-modified ethylenically unsaturated group-containing urethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, and a photopolymerization initiator.
<2> The acid-modified ethylenically unsaturated group-containing urethane resin has a weight average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3 The photosensitive composition according to <1>, which is 0.0 mmol / g and includes at least one of functional groups represented by the following general formulas (1) to (3) in a side chain.
However, in said general formula (1), R < ¹ > -R < ³ > represents either a hydrogen atom and a monovalent organic group each independently. X represents any of an oxygen atom, a sulfur atom, and —N (R ¹² ) —. R ¹² represents either a hydrogen atom or a monovalent organic group.
However, in said general formula (2), R < ⁴ > -R < ⁸ > represents either a hydrogen atom and a monovalent organic group each independently. Y represents an oxygen atom, a sulfur atom and -N ^{(R 12),} - represents either. R ¹² represents either a hydrogen atom or a monovalent organic group.
However, in said general formula (3), R < ⁹ > -R < ¹¹ > represents either a hydrogen atom and monovalent organic group each independently. Z represents an oxygen atom, a sulfur atom, -N (R 13) ^-, and represent any one of a phenylene group which may have a substituent. R ¹³ represents an alkyl group which may have a substituent.
<3> A part of acid groups of a copolymer obtained from an ethylenically unsaturated group-containing acrylic resin obtained from a compound having a (meth) acrylic acid ester and an ethylenically unsaturated group and having at least one acid group The photosensitive composition according to any one of <1> to <2>, wherein the copolymer is a modified copolymer obtained by adding (meth) acrylate having an epoxy group.
<4> The photosensitive composition according to any one of <1> to <3>, further containing a thermal crosslinking agent.
<5> The photosensitive composition according to any one of <1> to <4>, further including an inorganic filler.
<6> The ratio of the acid-modified ethylenically unsaturated group-containing urethane resin in the total mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin is 55% by mass or more and 95% by mass or less. The photosensitive composition according to any one of <1> to <5>.
<7> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <6> on a substrate.
<8> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <6>.
<9> A printed board comprising a permanent pattern formed by the method for forming a permanent pattern according to <8>.

  According to the present invention, it is possible to solve the conventional problems and achieve the object, and to provide a photosensitive composition excellent in insulation, thermal shock resistance, and resolution, and the photosensitive composition. The photosensitive laminate, the permanent pattern forming method, and the printed circuit board used can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least an acid-modified ethylenically unsaturated group-containing urethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, and a photopolymerization initiator, and further if necessary. And other components such as a thermal crosslinking agent and an inorganic filler.

<Acid-modified ethylenically unsaturated group-containing urethane resin>
The acid-modified ethylenically unsaturated group-containing urethane resin is not particularly limited as long as it is a urethane resin containing an acid group and an ethylenically unsaturated group, and can be appropriately selected according to the purpose. Examples of the acid group include a carboxyl group. Examples of the functional group having an ethylenically unsaturated group include an acryloyl group, a methacryloyl group, a vinylphenyl group, an allyl group, and a vinyl ether group.
Examples of the acid-modified ethylenically unsaturated group-containing urethane resin include (i) urethane resin having an ethylenically unsaturated group in the side chain, (ii) carboxyl group-containing polyurethane and epoxy group and ethylenically unsaturated in the molecule. Examples thereof include a urethane resin obtained by reacting a group-containing compound.

-(I) Urethane resin having an ethylenically unsaturated group in the side chain-
There is no restriction | limiting in particular as urethane resin which has an ethylenically unsaturated group in the said side chain, According to the objective, it can select suitably, For example, the following general formula (1)-(3) is given to the side chain. What has at least 1 among the functional groups represented is mentioned.

However, in said general formula (1), R < ¹ > -R < ³ > represents either a hydrogen atom and a monovalent organic group each independently.
Examples of R ^1, is not particularly limited and may be appropriately selected depending on the purpose, for example, a hydrogen atom, an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
The R ² and R ³ are not particularly limited and may be appropriately selected depending on the purpose. For example, each of R ² and R ³ is independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group. Group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryl which may have a substituent An oxy group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent Etc. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

In the general formula (1), X represents an oxygen atom, a sulfur atom, and -N ^{(R 12)} - represents one of the ^{R 12} represents any one of hydrogen atom, and a monovalent organic group . R ¹² is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  Here, the substituent that can be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom. Amino group, alkylamino group, arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like.

However, in said general formula (2), R < ⁴ > -R < ⁸ > represents either a hydrogen atom and a monovalent organic group each independently.
The R ^{4 to} R ⁸ are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, Nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

Examples of the substituent that can be introduced include the same as those in the general formula (1). Y represents any of an oxygen atom, a sulfur atom, and —N (R ¹² ) —. Wherein ^{R 12} has the same meaning as ^{R 12} in the general formula (1), and preferred examples are also the same.

However, in said general formula (3), R < ⁹ > -R < ¹¹ > represents either a hydrogen atom and monovalent organic group each independently.
Examples of R ^9, is not particularly limited and may be appropriately selected depending on the purpose, for example, an alkyl group which may have a hydrogen atom or a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
R ¹⁰ and R ¹¹ are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, Nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced include those similar to those in the general formula (1). Moreover, in said general formula (3), Z represents either an oxygen atom, a sulfur atom, -N (R < ¹³ >)-, and the phenylene group which may have a substituent. R ¹³ is an alkyl group which may have a substituent, and among these, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  The urethane resin having an ethylenically unsaturated group in the side chain includes at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5): A urethane resin having a basic unit as a structural unit represented by the reaction product of

OCN-X ⁰ -NCO: General formula (4)
^HO-Y 0 -OH ··· the general formula (5)
In the general formula (4) and the general formula (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

  At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If it has at least one, as a reaction product of the diisocyanate compound and the diol compound, a urethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is generated. Is done. According to the method, the urethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain, rather than replacing and / or introducing the desired side chain after the reaction of the urethane resin is generated. Can be easily manufactured.

  The diisocyanate compound represented by the general formula (4) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monofunctional alcohol or a monofunctional alcohol having a triisocyanate compound and an ethylenically unsaturated group may be used. Examples thereof include diisocyanate compounds that can be obtained by addition reaction with 1 equivalent of a functional amine compound.

  The triisocyanate compound is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438. Is mentioned.

  The monofunctional alcohol having the ethylenically unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraph “Japanese Patent Application Laid-Open No. 2005-250438” And compounds described in “0037” to “0040”.

  Here, the method for introducing an ethylenically unsaturated group into the side chain of the urethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. A method using a diisocyanate compound containing a polymerizable unsaturated group is preferred. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, A triisocyanate compound and the monofunctional alcohol which has an ethylenically unsaturated group, or 1 equivalent of monofunctional amine compounds are made to react. The diisocyanate compound which can be obtained by this, Comprising: The compound etc. which have an ethylenically unsaturated group in the side chain described in Paragraph "0042"-"0049" of Unexamined-Japanese-Patent No. 2005-250438 are mentioned, for example.

  The urethane resin having an ethylenically unsaturated group in the side chain contains the ethylenically unsaturated group from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. It is also possible to copolymerize diisocyanate compounds other than the diisocyanate compound.

The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a diisocyanate compound represented by the following general formula (6).
^OCN-L 1 -NCO ··· general formula (6)
In the general formula (6), L ¹ is a divalent aliphatic which may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Or represents an aromatic hydrocarbon group. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, for example, at least one of an ester group, a urethane group, an amide group, and a ureido group.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (6), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4 Aromatic diisocyanate compounds such as '-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4, 4' Alicyclic diisocyanate compounds such as methylene bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 Examples thereof include a diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a diol compound represented by the said General formula (5), According to the objective, it can select suitably, For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound etc. are mentioned.

  Here, as a method of introducing an ethylenically unsaturated group into the side chain of the urethane resin, a diol compound containing an ethylenically unsaturated group in the side chain is used as a raw material for urethane resin production in addition to the above-described method. The method used is also preferred. The diol compound containing an ethylenically unsaturated group in the side chain may be a commercially available compound such as trimethylolpropane monoallyl ether, or a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound. And compounds that are easily produced by reaction with a compound containing an ethylenically unsaturated group, such as a carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol, or a halogenated alkyl compound.

The diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs “0057” to “0060” of JP-A-2005-250438. And compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G). Among these, the compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G) are preferable.
In the general formula (G), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, wherein R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, ^R 1 to R ³ and X in the general formula (G) has the same meaning as ^R 1 to R ³ and X in the general formula (1), preferred embodiments versa.
By using the urethane resin derived from the diol compound represented by the general formula (G), the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance is suppressed, and the coating strength of the layer is increased. It is thought that improvement can be achieved.

The urethane resin having an ethylenically unsaturated group in the side chain is, for example, ethylenic in the side chain from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. A diol compound other than a diol compound containing an unsaturated group can be copolymerized.
The diol compound other than the diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol Compound etc. are mentioned.

  There is no restriction | limiting in particular as said polyether diol compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0068"-"0076" of Unexamined-Japanese-Patent No. 2005-250438 etc. are mentioned. It is done.

  There is no restriction | limiting in particular as said polyester diol compound, According to the objective, it can select suitably, For example, Paragraph "0077"-"0079" of Unexamined-Japanese-Patent No. 2005-250438, Paragraph "0083"-"0085" No. 1-No. 8 and no. 13-No. 18 and the like.

  There is no restriction | limiting in particular as said polycarbonate diol compound, According to the objective, it can select suitably, For example, Unexamined-Japanese-Patent No. 2005-250438 Paragraph "0080"-"0081" and Paragraph "0084" No. 9-No. 12 and the like.

Moreover, in the synthesis | combination of the urethane resin which has an ethylenically unsaturated group in the said side chain, the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
The diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0087” to “0088” of JP-A-2005-250438 And the compounds described.

  Furthermore, in the synthesis | combination of the urethane resin which has an ethylenically unsaturated group in the said side chain, the diol compound which has a carboxyl group other than the diol compound mentioned above can also be used together. The diol compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds represented by the following general formulas (8) to (10).

In the general formula (8), R ¹⁵ is a hydrogen atom, a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH _2. , —COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, or aralkyl having 7 to 15 carbon atoms) Each group such as an alkyl group which may have a substituent, an aralkyl group which may have the substituent, an aryl group which may have the substituent, The alkoxy group which may have the said substituent and the aryloxy group which may have the said substituent are represented. Among these, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
In the general formulas (8) to (10), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl). A divalent aliphatic or aromatic hydrocarbon group optionally having a group, an alkoxy group, or a halogeno group. Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, the L ^{9 to} L ¹¹ may have other functional groups that do not react with the isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, and an ether group. . In addition, you may form a ring by 2 or 3 of said R < ¹⁵ >, L < ⁷ >, L < ⁸ >, L < ⁹ >.
In the general formula (9), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose. An aromatic group having 6 to 15 carbon atoms is preferable.

  There is no restriction | limiting in particular as a diol compound which has a carboxyl group represented by the said General formula (8)-(10), According to the objective, it can select suitably, For example, 3, 5- dihydroxy benzoic acid, 2 , 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4- Hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) ) -3-carboxy-propionamide and the like.

The presence of such a carboxyl group is preferable in that the urethane resin can be provided with properties such as hydrogen bonding properties and alkali solubility. More specifically, the urethane resin having an ethylenically unsaturated group in the side chain is a resin having a carboxyl group in the side chain, and more specifically, the ethylenically unsaturated group in the side chain is 0. It is preferably 0.05 mmol / g to 3.0 mmol / g, more preferably 0.5 mmol / g to 2.7 mmol / g, and particularly preferably 0.75 mmol / g to 2.4 mmol / g. Preferably, the side chain has a carboxyl group, and the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and 35 mgKOH / g to 100 mg KOH / g is particularly preferred.
In addition, the said acid value can be measured based on JISK0070, for example. However, when the sample does not dissolve, dioxane or tetrahydrofuran is used as a solvent.

Moreover, in the synthesis | combination of the urethane resin which has an ethylenically unsaturated group in the said side chain, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-2005-250438, paragraph "0095" And the compounds described in “0101”.

The urethane resin having an ethylenically unsaturated group in the side chain is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent by adding a known catalyst having an activity depending on the reactivity and heating. Is done. The molar ratio of diisocyanate and diol compound used for synthesis (M _a : M _b ) is not particularly limited and may be appropriately selected depending on the intended purpose, preferably 1: 1 to 1.2: 1. By treating with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.

  Moreover, as a urethane resin which has an ethylenically unsaturated group in the said side chain, what has an ethylenically unsaturated group in a polymer terminal and a principal chain is used suitably. By having an ethylenically unsaturated group at the polymer terminal and main chain, it further has an ethylenically unsaturated group between the photosensitive composition and the urethane resin having an ethylenically unsaturated group in the side chain, or in the side chain. Crosslinking reactivity is improved between urethane resins, and the strength of the photocured product is increased. As a result, when a urethane resin having an ethylenically unsaturated group in the side chain is used for a lithographic printing plate, a material having excellent toughness can be provided.

Examples of the method for introducing an ethylenically unsaturated group at the polymer terminal include the following methods. That is, in the step of synthesizing a urethane resin having an ethylenically unsaturated group in the side chain as described above, in the step of treating with a residual isocyanate group at the polymer terminal and an alcohol or an amine, it has an ethylenically unsaturated group. Alcohols or amines may be used.
Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an ethylenically unsaturated group.
The ethylenically unsaturated group is preferably introduced into the polymer side chain rather than the polymer end from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and the crosslinking reaction efficiency is improved. .

The functional group having an ethylenically unsaturated group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, a vinylphenyl group The methacryloyl group and the acryloyl group are more preferable, and the methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.

  As a method for introducing an ethylenically unsaturated group into the main chain, there is a method of using a diol compound having an ethylenically unsaturated group in the main chain direction for the synthesis of a urethane resin. The diol compound having an ethylenically unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-2-butene-1,4-diol and trans-2-butene. -1,4-diol, polybutadiene diol and the like.

  The urethane resin having an ethylenically unsaturated group in the side chain can be used in combination with an alkali-soluble polymer containing a urethane resin having a structure different from that of the specific urethane resin. For example, the urethane resin having an ethylenically unsaturated group in the side chain can be used in combination with a urethane resin containing an aromatic group in the main chain and / or side chain.

  Specific examples of the urethane resin (i) having an ethylenically unsaturated group in the side chain include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. And 31 polymers. Among these, the polymers of P-27 and P-28 shown in paragraphs “0308” and “0309” are preferable.

-(Ii) Urethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule-
The urethane resin obtained by reacting the carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule includes a carboxyl group-containing polyurethane having a diisocyanate and a carboxylic acid group-containing diol as essential components; A urethane resin obtained by reacting an epoxy group and a compound having an ethylenically unsaturated group in the molecule. Depending on the purpose, a low molecular diol having a weight average molecular weight of 300 or less or a low molecular diol having a weight average molecular weight of 500 or more may be added as a copolymer component as a diol component.
By using the urethane resin, it is excellent in stable dispersibility with an inorganic filler, crack resistance and impact resistance, so that heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties are improved.

  In addition, as the urethane resin, a divalent aliphatic and aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via either a C atom or an N atom. A reaction product containing a carboxylic acid-containing diol as an essential component, and reacting the obtained reaction product with a compound having an epoxy group and an ethylenically unsaturated group in the molecule through a —COO— bond. It may be obtained.

Moreover, as said urethane resin, at least 1 sort (s) chosen from the diisocyanate shown by the following general formula (11), and the carboxylic acid group containing diol shown by the following general formula (12-1)-(12-3), And at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by the following general formulas (13-1) to (13-5) according to the purpose: The reaction product obtained is reacted with a compound having an epoxy group and an ethylenically unsaturated group in the molecule represented by the following general formulas (14-1) to (14-16). It may be obtained.
However, in the general formula (11), R ₁ may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Represents an aromatic or aromatic hydrocarbon. If necessary, R ₁ may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group. In the general formula (12-1), R ₂ represents a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH ₂ , — COOR ₆ , —OR ₆ , —NHCONHR ₆ , —NHCOOR ₆ , —NHCOR ₆ , —OCONHR ₆ , —CONHR ₆ (where R ₆ is an alkyl group having 1 to 10 carbon atoms, aralkyl having 7 to 15 carbon atoms) Each group is included), an aralkyl group that may have the substituent, and an aryl that may have the substituent A group, an alkoxy group which may have the substituent, or an aryloxy group which may have the substituent; Among these, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable. In the general formulas (12-1), (12-2) and (12-3), R ₃ , R ₄ and R ₅ may be the same or different from each other, and may be a single bond or a substituent (for example, , An alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group are preferable), and may represent a divalent aliphatic or aromatic hydrocarbon. Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, in R ₃ , R ₄ and R ₅ , any other functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have. In addition, you may form a ring by 2 or 3 of said R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ >. Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and an aromatic group having 6 to 15 carbon atoms is preferable.

However, in the general formulas (13-1) to (13-3), R ₇ , R ₈ , R ₉ , R _10, and R ₁₁ may be the same or different, and may be divalent. Represents an aliphatic or aromatic hydrocarbon. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon having 2 to 10 carbon atoms. Several to 10 arylene groups are more preferable. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is More preferred. In addition, in R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups , An amide group, a ureido group, or a halogen atom.
In the general formula (13-4), R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group, or a halogen atom. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ˜6 alkyl and aryl groups having 6 to 10 carbon atoms. R ₁₂ may have other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms.
In the general formula (13-5), R ₁₃ represents an aryl group or a cyano group, and preferably an aryl group or a cyano group having 6 to 10 carbon atoms. In the general formula (13-4), m represents an integer of 2 to 4. In the general formulas (13-1) to (13-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represent an integer of 2 or more, and an integer of 2 to 100 is preferable. In the general formula (13-5), n ₆ represents 0 or an integer of 2 or more, and 0 or an integer of 2 to 100 is preferable.

In the general formula _{(14-1) ~ (14-16),} R 14 represents a hydrogen atom or a methyl _{group, R 15} represents an alkylene group having 1 to 10 carbon _{atoms, R 16} is a carbon The hydrocarbon group of number 1-10 is represented. p represents 0 or an integer of 1 to 10.

  In addition, the urethane resin may be copolymerized with a low molecular weight diol that does not contain a carboxylic acid group as another component, and as the low molecular weight diol, the general formulas (13-1) to (13-5) may be used. The weight average molecular weight is 500 or less. The low molecular weight diol containing no carboxylic acid group can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.

  As the urethane resin, in particular, a diisocyanate represented by the general formula (11) and at least one selected from carboxylic acid group-containing diols represented by the general formulas (12-1) to (12-3) are essential. As a component, depending on the purpose, at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by general formulas (13-1) to (13-5), In addition to the reaction product of the low molecular weight diol containing no carboxylic acid group having a weight average molecular weight of 500 or less represented by the formulas (13-1) to (13-5), the formulas (14-1) to (14-16) ), Which is obtained by reacting a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any one of the above, an alkali acid having an acid value of 20 mgKOH / g to 120 mgKOH / g. Sex photocrosslinkable urethane resin is preferable.

  These polymer compounds may be used alone or in combination of two or more.

--Method of synthesizing urethane resin obtained by reacting carboxyl group-containing polyurethane with compound having epoxy group and ethylenically unsaturated group in molecule--
As a method for synthesizing the urethane resin, the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, the molar ratio of the diisocyanate and diol compound can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.

--Diisocyanate--
There is no restriction | limiting in particular as a diisocyanate compound shown by the said General formula (11), According to the objective, it can select suitably, For example, the compound described in Paragraph "0021" of Unexamined-Japanese-Patent No. 2007-2030 etc. Is mentioned.

--High molecular weight diol--
The high molecular weight diol compound represented by the general formulas (13-1) to (13-5) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as disclosed in JP-A-2007-2030 Examples thereof include compounds described in paragraphs “0022” to “0046”.

--Carboxylic acid group-containing diol--
In addition, the diol compound having a carboxyl group represented by the general formulas (12-1) to (12-3) is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in paragraph “0047” of No. 2030 publication.

--Carboxylic acid group-free low molecular weight diol--
The carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0048” of JP2007-2030A. It is done.
The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80% or less, and particularly preferably 50% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.

  Specific examples of the urethane resin obtained by reacting the above (ii) carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule include, for example, paragraph “Japanese Patent Application Laid-Open No. 2007-2030”. Glycidyl acrylate as a compound containing an epoxy group and an ethylenically unsaturated group in the polymers of U1 to U13, U1 to U4 and U6 to U11 shown in "0314" to "0315" is converted into glycidyl methacrylate, 3,4-epoxycyclohexylmethyl. Examples thereof include polymers in place of acrylate (trade name: Cyclomer A400 (manufactured by Daicel Chemical Industries)) and 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical Industries)).

-Weight average molecular weight of acid-modified ethylenically unsaturated group-containing urethane resin-
There is no restriction | limiting in particular as a weight average molecular weight of the said acid-modified ethylenically unsaturated group containing urethane resin, Although it can select suitably according to the objective, 2,000-60,000 are preferable, 3,000-50 3,000 is more preferable, and 3,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 2,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may be deteriorated. . On the other hand, when the photosensitive resin composition is used as a photosensitive solder resist when the weight average molecular weight is 2,000 to 60,000, it is excellent in crack resistance and heat resistance, and is a non-image part by an alkaline developer. Excellent developability.
The weight average molecular weight is, for example, a high-speed GPC device (HLC-802A manufactured by Toyo Soda Kogyo Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column of one TSKgel HZM-M. 200 μL of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).

-Acid value of acid-modified ethylenically unsaturated group-containing urethane resin urethane resin-
The acid value of the acid-modified ethylenically unsaturated group-containing urethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 mgKOH / g to 120 mgKOH / g, preferably 30 mgKOH / g to 110 mgKOH / g is more preferable, and 35 mgKOH / g to 100 mgKOH / g is particularly preferable. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development rate may be too high, and development control may be difficult.
In addition, the said acid value can be measured based on JISK0070, for example. However, when the sample does not dissolve, dioxane or tetrahydrofuran is used as a solvent.

-Equivalent ethylenically unsaturated group of acid-modified ethylenically unsaturated group-containing urethane resin-
The ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing urethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mmol / g to 3 mmol / g, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable. When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 3 mmol / g, the brittleness of the cured film may increase.
The said ethylenically unsaturated group equivalent can be calculated | required by measuring a bromine number, for example. The bromine number can be measured according to, for example, JIS K2605.

-Content of acid-modified ethylenically unsaturated group-containing urethane resin-
As a ratio of the acid-modified ethylenically unsaturated group-containing urethane resin in the total mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition, in particular, There is no restriction | limiting, Although it can select suitably according to the objective, 55 mass%-95 mass% are preferable, and 65 mass%-75 mass% are more preferable. When the ratio is less than 55% by mass, the thermal shock resistance may be lowered, and when it exceeds 95% by mass, the insulation may be lowered. When the ratio is within the more preferable range, it is advantageous in that both insulation and thermal shock resistance are very excellent.

<Ethylenically unsaturated group-containing acrylic resin>
The ethylenically unsaturated group-containing acrylic resin is not particularly limited as long as it is an acrylic resin containing an ethylenically unsaturated group that can be polymerized by radicals generated by a photopolymerization initiator, and is appropriately selected depending on the purpose. be able to. Examples of the functional group having an ethylenically unsaturated group include an acrylate group, a methacrylate group, an allyl group, a vinyl ether group, and a vinylphenyl group.
As said ethylenically unsaturated group containing acrylic resin, the copolymer (B) which has (meth) acrylic acid ester (A) and a compound (B) which has an ethylenically unsaturated group and has at least 1 acid group ( Hereinafter, a modified copolymer obtained by adding (meth) acrylate (C) having an epoxy group to a part of acid groups of “copolymer” (hereinafter referred to as “modified copolymer”) It is preferable from the point of being excellent in heat resistance.
In the present invention, (meth) acrylic acid ester means acrylic acid ester and methacrylic acid ester, and (meth) acrylate means acrylate and methacrylate.

-(Meth) acrylic acid ester (A)-
Examples of the (meth) acrylic acid ester (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate. (Meth) acrylic acid alkyl esters such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate and other hydroxyl groups ( Meth) acrylic acid esters; benzyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (me ) Acrylate, phenoxy triethyleneglycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, etc. (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. Among these, benzyl (meth) acrylate is preferable in terms of low water absorption.

-Compound (B) containing an ethylenically unsaturated group and having at least one acid group-
Examples of the compound (B) containing an ethylenically unsaturated group and having at least one acid group include a chain extension between acrylic acid, methacrylic acid, vinylphenol, and ethylenically unsaturated group and carboxylic acid. Modified unsaturated monocarboxylic acid.
Examples of the modified unsaturated monocarboxylic acid chain-extended between the ethylenically unsaturated group and the carboxylic acid include β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalate. Examples thereof include acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond such as lactone modification, and modified unsaturated monocarboxylic acid having an ether bond.
These may be used individually by 1 type and may use 2 or more types together.

--Lactone modified unsaturated monocarboxylic acid--
Specific examples of the lactone-modified unsaturated monocarboxylic acid include compounds obtained by lactone modification of (meth) acrylic acid and represented by the following formula (1).
_{^{CH 2 = C (-R 1)}} CO- [O (CR 2 R 3) m CO] n -OH ·· (1)
In addition, a lactone-modified product obtained by acid-modifying a terminal hydroxyl group with an acid anhydride and a compound represented by the following formula (2) can be given.
CH ₂ ═C (—R ¹ ) COO—CH ₂ CH ₂ O [CO (CR ² R ³ ) _m O] _n COR ⁴ COOH (2)
However, the formula (1), in (2), ^{R 1} is represents a hydrogen atom or a methyl group. m R ² and R ³ each independently represent any of a hydrogen atom, a methyl group, and an ethyl group, and may be different from each other. R ⁴ is a C 1-10 divalent aliphatic saturated hydrocarbon group, a C 2-10 divalent unsaturated hydrocarbon group, a C 3-6 divalent alicyclic saturated hydrocarbon. Represents any of a group, an unsaturated hydrocarbon group having 3 to 6 carbon atoms, a p-xylylene group, and a phenylene group. m represents an integer of 4 to 8, and n represents an integer of 1 to 10.

--Modified unsaturated monocarboxylic acid having an ether bond--
As the modified unsaturated monocarboxylic acid having an ether bond, for example, an epoxy compound such as ethylene oxide is added to (meth) acrylic acid, and the molecular terminal hydroxyl group of the adduct is an acid-modified product with an acid anhydride. The compound represented by Formula (3) is mentioned.
_{^{CH 2 = C (-R 1)}} COO - [(CR 2 R 3) m O] n -COR 4 COOH (3)
However, in the formula (3), R ¹ represents a hydrogen atom or a methyl group. m R ² and R ³ each independently represents any of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, and may be different from each other. R ⁴ is a C 1-10 divalent aliphatic saturated hydrocarbon group, a C 2-10 divalent unsaturated hydrocarbon group, a C 3-6 divalent alicyclic saturated hydrocarbon. A group, and a C 3-6 divalent unsaturated hydrocarbon group, p-xylylene, and a phenylene group. m and n represent an integer of 1 to 10.

-(Meth) acrylate having epoxy group (C)-
The (meth) acrylate (C) having an epoxy group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth). An acrylate etc. are mentioned. Among these, glycidyl (meth) acrylate is preferable.

-Method for producing modified copolymer-
As a method for producing the ethylenically unsaturated group-containing acrylic resin, an example of the method for producing the modified copolymer will be described below.
First, the copolymer is produced. There is no restriction | limiting in particular as a manufacturing method of the said copolymer, According to the objective, it can select suitably, For example, the manufacturing methods of well-known acrylic resins, such as solution polymerization, are mentioned.
Subsequently, the modified copolymer is produced by adding the (meth) acrylate (C) having the epoxy group to some of the acid groups of the copolymer.
There is no restriction | limiting in particular as said additional amount, According to the objective, it can select suitably.
In the addition, it is preferable to use a solvent and a catalyst.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, the solvent etc. of Paragraph [0020] of Unexamined-Japanese-Patent No. 2009-086376 are mentioned.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, the catalyst etc. of Paragraph [0021]-[0025] of Unexamined-Japanese-Patent No. 2009-086376 are mentioned.

  There is no restriction | limiting in particular as an acid value of the said ethylenically unsaturated group containing acrylic resin, Although it can select suitably according to the objective, 10 mgKOH / g-150 mgKOH / g is preferable, 50 mgKOHg / g-150 mgKOH / g is More preferred. When the acid value is less than 10 mgKOH / g, it may be difficult to remove the uncured film with a dilute alkaline aqueous solution, and when it exceeds 150 mgKOH / g, the water resistance and electrical characteristics of the cured film may be inferior. is there.

  There is no restriction | limiting in particular as a weight average molecular weight of the said ethylenically unsaturated group containing acrylic resin, Although it can select suitably according to the objective, 5,000-100,000 are preferable. When the weight average molecular weight is less than 5,000, the tack-free performance is inferior, the moisture resistance of the coated film after exposure is poor, film slippage occurs during development, and the resolution is greatly inferior. When the weight average molecular weight exceeds 100,000, developability may be remarkably deteriorated and storage stability may be inferior.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said ethylenically unsaturated group containing acrylic resin, Although it can select suitably according to the objective, 1 mass%-30 mass% are preferable, 2 mass%-25 mass% are more preferable.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has one or more functional groups which have an ethylenically unsaturated group is preferable.

  Examples of the functional group having an ethylenically unsaturated group include a (meth) acryloyl group, a (meth) acrylamide group, a vinylphenyl group, a vinyl ester group, a vinyl ether group, an allyl ether group, and an allyl ester group.

  There is no restriction | limiting in particular as a compound which has one or more functional groups which have the said ethylenically unsaturated group, Although it can select suitably according to the objective, At least 1 selected from the monomer which has a (meth) acryl group. Species are preferred.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Tri (meth) acrylate; polyfunctional alcohols such as trimethylolpropane, glycerin, bisphenol, etc., after addition reaction of ethylene oxide and propylene oxide, (meth) acrylate; reaction reaction of epoxy resin and (meth) acrylic acid Examples thereof include polyfunctional acrylates such as epoxy acrylates and methacrylates. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said polymeric compound, Although it can select suitably according to the objective, 5 mass%-50 mass% are preferable, and 10 mass%- 40 mass% is more preferable. When the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Those having photosensitivity are preferable, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of monomer. May be.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.
As said photoinitiator, a neutral photoinitiator is preferable. Moreover, the other photoinitiator may be included as needed.

  The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a compound having at least an aromatic group, such as (bis) acylphosphine oxide or an ester thereof. More preferred are acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds. Two or more neutral photopolymerization initiators may be used in combination.

  Examples of the photopolymerization initiator include (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, and thiols. Compound etc. are mentioned. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, oxime derivatives, (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone Compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.

  Examples of the (bis) acylphosphine oxide, the acetophenone compound, the benzophenone compound, the benzoin ether compound, the ketal derivative compound, and the thioxanthone compound include, for example, paragraph [0042] of JP 2010-256399 A Examples thereof include (bis) acylphosphine oxides, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds.

  Examples of the oxime derivative include oxime derivatives described in paragraphs [0043] to [0059] of JP2010-256399A.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0 More preferably, the content is more preferably 5% by mass to 20% by mass, and particularly preferably 0.5% by mass to 15% by mass.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. An epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), an oxetane compound having at least two oxetanyl groups in one molecule can be used, and is described in JP-A-2007-47729. A compound obtained by reacting a blocking agent with an isocyanate group of an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate or a derivative thereof ( Blocked polyisocyanate compound).

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 3 mass%- 30 mass% is more preferable. If the said content is 1 mass% or more, the film | membrane intensity | strength of a cured film will be improved, and if it is 50 mass% or less, developability and exposure sensitivity will become favorable.

  Examples of the epoxy compound include epoxy compounds described in paragraphs [0071] to [0073] of JP2010-256399A.

  Examples of the oxetane compound include oxetane compounds described in paragraph [0074] of JP2010-256399A.

  Examples of the polyisocyanate compound include the polyisocyanate compounds described in paragraph [0075] of JP2010-256399A.

  Examples of the blocked polyisocyanate compound include the blocked polyisocyanate compound described in paragraph [0076] of JP2010-256399A.

  Examples of the melamine derivative include melamine derivatives described in paragraph [0077] of JP 2010-256399 A.

<Inorganic filler>
The photosensitive resin composition preferably contains an inorganic filler. The inorganic filler can improve the surface hardness of the permanent pattern, keep the coefficient of linear expansion low, or keep the dielectric constant and dielectric loss tangent of the cured film itself low.
Examples of the inorganic filler include kaolin, barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica. As a commercial item of the said barium sulfate, B-30 (made by Sakai Chemical Industry Co., Ltd.) etc. are mentioned, for example.
Among these, silica, barium sulfate, talc, and aluminum hydroxide are preferable, and silica is more preferable.

  There is no restriction | limiting in particular as an average particle diameter of the said inorganic filler, Although it can select suitably according to the objective, Less than 10 micrometers is preferable and 3 micrometers or less are more preferable. When the average particle size is 10 μm or more, resolution may be deteriorated due to light confusion.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said inorganic filler, Although it can select suitably according to the objective, 1 mass%-60 mass% are preferable. When the content is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced. When the content exceeds 60% by mass, the cured film is formed when a cured film is formed on the surface of the photosensitive layer. When the wiring is formed using a permanent pattern, the function as a protective film for the wiring may be impaired.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and a colorant (color pigment or dye). Furthermore, adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers. , Chain transfer agent, etc.) may be used in combination.
By appropriately containing these components, properties such as stability, photographic properties, and film properties of the intended photosensitive composition can be adjusted.
Examples of the thermal polymerization inhibitor include thermal polymerization inhibitors described in paragraphs [0101] to [0102] of JP-A-2008-250074.
Examples of the thermosetting accelerator include the thermosetting accelerator described in paragraph [0093] of JP-A-2008-250074.
Examples of the plasticizer include the plasticizers described in paragraphs [0103] to [0104] of JP-A-2008-250074.
Examples of the colorant include the colorants described in paragraphs [0105] to [0106] of JP-A-2008-250074.
Examples of the adhesion promoter include adhesion promoters described in paragraphs [0107] to [0109] of JP-A-2008-250074.

  There is no restriction | limiting in particular as a usage form of the said photosensitive composition, According to the objective, it can select suitably, You may use it in a liquid state and may use it as a photosensitive film.

<Photosensitive film>
The said photosensitive film has a support body and the photosensitive layer which contains the photosensitive composition of this invention on this support body at least, and also has another layer as needed.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  There is no restriction | limiting in particular as said support body, According to the objective, it can select suitably, For example, the support body of Paragraph [0115]-[0117] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

-Photosensitive layer-
If the said photosensitive layer is a layer which consists of the said photosensitive composition of this invention, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.

  As a method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support, and the solution is directly applied. The method of laminating | stacking by apply | coating and drying is mentioned.

  There is no restriction | limiting in particular as a solvent used for the said photosensitive composition solution, According to the objective, it can select suitably.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating etc. are mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-30 micrometers are especially preferable.

-Other layers-
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, etc. Layer. The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.

--Protective film--
The photosensitive film may form a protective film on the photosensitive layer.
There is no restriction | limiting in particular as said protective film, According to the objective, it can select suitably, For example, the protective film as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.
There is no restriction | limiting in particular as a combination of the said protective film and the said support body, According to the objective, it can select suitably, For example, the combination as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned. It is done.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

  There is no restriction | limiting in particular as the length of the said photosensitive film, and a storage method, According to the objective, it can select suitably, For example, the length and storage as described in Paragraph [0120] of Unexamined-Japanese-Patent No. 2008-250074. The method etc. are mentioned.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying it at 30 to 150 ° C. for 1 to 30 minutes. As for the temperature in the case of the said drying, 50 to 120 degreeC is especially preferable.

(Photosensitive laminate)
The photosensitive laminate of the present invention comprises at least a substrate and a photosensitive layer on the substrate, and further laminates other layers as necessary.
The photosensitive layer is a layer containing the photosensitive composition of the present invention.
The photosensitive layer is, for example, transferred from the photosensitive film produced by the above-described manufacturing method, and has the same configuration as described above.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

<Method for producing photosensitive laminate>
The method for producing the photosensitive laminate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of heating and pressing at least the photosensitive layer in the photosensitive film of the present invention is performed. And a method of transferring and laminating.

An example of the manufacturing method of the said photosensitive laminated body is the method of laminating | stacking the photosensitive film of this invention on the surface of the said base | substrate, performing at least any one of a heating and pressurization. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator Co., Ltd. make, VP-II, Nichigo Morton Co., Ltd. make, VP130) is preferable.

  The photosensitive film and the photosensitive laminate of the present invention can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be particularly suitably used for forming a permanent pattern on a printed circuit board.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps as necessary.

<Exposure process>
The exposure step is not particularly limited as long as it is a step of exposing the photosensitive layer formed of the photosensitive composition of the present invention, and can be appropriately selected according to the purpose. The process of exposing with respect to the photosensitive layer in the said photosensitive laminated body is mentioned.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose, but while performing at least one of heating and pressurizing the photosensitive film on the substrate. It is preferable to be performed on a laminated body formed by laminating.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, For example, digital exposure, analog exposure, etc. are mentioned.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.

-Development process-
The developing step is a step of removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as a removal method of the said exposed part, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, the developing solution as described in Paragraph [0171]-[0173] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

  The method for the entire surface exposure treatment and the entire surface heat treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, in paragraphs [0176] to [0177] of JP-A-2008-250074 The method of description is mentioned.

When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on a printed circuit board by the permanent pattern forming method. Then, soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

(Printed board)
The printed circuit board of the present invention comprises at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
There is no restriction | limiting in particular as another structure, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples at all.

In addition, the acid value, weight average molecular weight, and ethylenically unsaturated group equivalent in the synthesis examples were measured by the following methods.
<Acid value>
The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
<Weight average molecular weight>
The weight average molecular weight is determined by using a high-speed GPC device (HLC-802A manufactured by Toyo Soda Industry Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column using one TSKgel HZM-M, A 200 μL sample was injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength: 254 nm).
<Equivalent ethylenically unsaturated group>
The said ethylenically unsaturated group equivalent was calculated | required by measuring a bromine number based on JISK2605.

(Synthesis Example 1)
<Synthesis of acid-modified ethylenically unsaturated group-containing urethane resin 1>
A 500 mL three-necked round bottom flask equipped with a condenser and a stirrer was charged with 10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g of glycerol monomethacrylate (GLM). (0.105 mol) was dissolved in 79 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, and a catalyst: Neostan U-600 (Nitto) (Made by Kasei Co., Ltd.) 0.2g was added, and it stirred at 75 degreeC for 5 hours. Thereafter, the mixture was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of an acid-modified ethylenically unsaturated group-containing urethane resin 1 solution (solid content: 40% by mass).
The acid-modified ethylenically unsaturated group-containing urethane resin 1 obtained above has a solid content acid value of 70 mgKOH / g and a weight average molecular weight (polystyrene standard) of 8 measured by gel permeation chromatography (GPC). And the ethylenically unsaturated group equivalent was 1.5 mmol / g.

(Synthesis Example 2)
<Synthesis of acid-modified ethylenically unsaturated group-containing urethane resin 2>
In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 32.00 g (0.216 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMBA) and polypropylene glycol (molecular weight 1,000) 9.0 g (0.009 mol) of (PPG1000) was dissolved in 118 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, 0.2 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) After stirring at 75 ° C. for 5 hours, 9.61 g of methyl alcohol was added. Thereafter, 17.91 g (0.126) of glycidyl methacrylate (GMA) as an ethylenically unsaturated group-containing epoxy and 5,000 ppm of triphenylphosphine as a catalyst were further added, and the mixture was stirred at 110 ° C. for 5 hours. Then, 214 g of acid-modified ethylenically unsaturated group-containing urethane resin 2 solution (solid content: 40% by mass) was obtained.
The acid-modified ethylenically unsaturated group-containing urethane resin 2 obtained above has a solid content acid value of 75 mgKOH / g and a weight average molecular weight (polystyrene standard) of 12 measured by gel permeation chromatography (GPC). And the ethylenically unsaturated group equivalent was 1.3 mmol / g.

(Synthesis Example 3)
<Synthesis of ethylenically unsaturated group-containing acrylic resin 1>
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 3.0 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (30 mol% / 70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and dissolved by stirring. After dissolution, 3.0 g of triphenylphosphine was added while performing air bubbling, heated to 100 ° C., and after 20 minutes, glycidyl methacrylate was added to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to obtain an ethylenically unsaturated group-containing acrylic resin 1 solution represented by the following structural formula having a solid content of 40% by mass.

-Ethylenically unsaturated group-containing acrylic resin 1
However, * 1 in the ethylenically unsaturated group-containing acrylic resin 1 represents a mixture of the structure represented by the following structural formula (a) and the structure represented by the following structural formula (b) (mixing ratio is unknown). .

(Synthesis Example 4)
<Synthesis of urethane resin 1>
A 300 mL three-necked round bottom flask equipped with a condenser and a stirrer was charged with 21.73 g (0.162 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and polypropylene glycol (Mw 1,000, PPG 1000). 30.00 g (0.030 mol) and 12.78 g (0.168 mol) of propylene glycol (PG) were dissolved in 202 mL of propylene glycol monomethyl ether monoacetate. To this, 60.06 g (0.24 mol) of 4,4-diphenylmethane diisocyanate (MDI), 10.09 g (0.06 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene 0 As a catalyst, 0.4 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 75 ° C. for 5 hours. Next, the mixture was stirred at room temperature for 30 minutes to obtain 336 g of a urethane resin 1 solution (solid content: 40% by mass).
The obtained urethane resin 1 had a solid content acid value of 67 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 8,000.

(Synthesis Example 5)
<Synthesis of acrylic resin 1>
In a five-neck reaction vessel with an internal volume of 2 L, 800 g of propylene glycol monomethyl ether acetate (PGMAc), 140 g of butyl methacrylate (BMA), 30 g of methacrylic acid (MAA), 30 g of hydroxyethyl methacrylate (HEMA), methyl azobisisobutyrate (V -601, manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 80 ° C. for 6 hours while blowing nitrogen to obtain an acrylic resin 1 solution. Then, it concentrated and obtained the acrylic resin 1 solution with a solid content of 40 mass%. The obtained acrylic resin 1 had a weight average molecular weight of 10,000.

Example 1
<Manufacture of photosensitive film>
On a 16 μm thick polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) as a support, a photosensitive composition solution having the following composition is applied and dried to form a 30 μm thick photosensitive layer on the support. did. On the photosensitive layer, a 20 μm-thick polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated as a protective layer to produce a photosensitive film.

-Composition of photosensitive composition solution-
-Acid-modified ethylenically unsaturated group-containing urethane resin 1 solution of Synthesis Example 1 (solid content 40 mass%) ... 75.02 parts by mass-Ethylenically unsaturated group-containing acrylic resin 1 solution of Synthesis Example 3 (solid content) 40 mass%) ... 11.58 parts by mass Polymerizable compound (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) ... 18.97 parts by mass Thermal crosslinking agent (Epototo YDF-170, manufactured by Toto Kasei Co., Ltd., bisphenol) F-type epoxy resin) ... 10.34 parts by mass-Elastomer (manufactured by Hitachi Chemical Co., Ltd., MFGAc 15% by mass solution) ... 29.27 parts by mass-Irgacure 907 ... 2.07 parts by mass-EAB -F (made by Hodogaya Chemical Co., Ltd.): 0.069 parts by mass DETX-S (made by Nippon Kayaku): 0.020 parts by mass Pigment dispersion (hereinafter referred to as “G-1”)・ 77.10 parts by mass -Cyclohexanone (solvent) ... 6.76 parts by mass The pigment dispersion (G-1) is 16.08 parts by mass of silica (manufactured by Admatechs, SO-C2), and the acid modification of Synthesis Example 1 29.05 parts by mass of ethylenically unsaturated group-containing urethane resin 1 solution, 0.074 parts by mass of phthalocyanine blue, 0.021 parts by mass of anthraquinone yellow pigment (CI.PY24), and 0.57 parts by mass of melamine Then, 2.95 parts by mass of IXE6107 (manufactured by Tohto Kasei) and 28.35 parts by mass of cyclohexanone were mixed in advance, and with a motor mill M-250 (manufactured by Eiger), zirconia beads having a diameter of 1.0 mm were used. It was prepared by dispersing for 3 hours at a speed of 9 m / s.
In the photosensitive composition, the ratio of the acid-modified ethylenically unsaturated group-containing urethane resin 1 in the total mass of the acid-modified ethylenically unsaturated group-containing urethane resin 1 and the ethylenically unsaturated group-containing acrylic resin 1 is It was 90% by mass.

-Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through holes, copper thickness 12 μm) to chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were as follows: a vacuuming time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 10 seconds.

-Exposure process-
A predetermined pattern is obtained with a parallel light exposure machine (ultra-high pressure mercury lamp) from the polyethylene terephthalate film (support) side through a glass mask having a predetermined pattern with respect to the photosensitive layer in the prepared photosensitive laminate. Irradiation was performed with an energy amount of 60 mJ / cm ² to cure a part of the photosensitive layer.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1% by mass sodium carbonate aqueous solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Was spray-developed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the laminate on which the permanent pattern is formed is subjected to a heat treatment at 150 ° C. for 1 hour, and then subjected to post-exposure under the condition of 1 J / cm ² to cure the surface of the permanent pattern and to improve the film strength. Raised and produced a test plate.

<Evaluation>
Insulation, thermal shock resistance, and resolution were evaluated as follows. The results are shown in Table 1.

<< Insulation >>
In the lamination to the substrate, the lamination on the substrate, the exposure step, the development step, and the like, except that the copper-clad laminate was replaced with a comb substrate having a copper thickness of 12 μm and L / S = 25 μm / 25 μm. A curing process was performed to produce an evaluation substrate.
Using the evaluation substrate, a super accelerated high temperature high humidity life test (HAST) was performed under the conditions of 130 ° C., 85% RH, 50 V, 200 hours.
Thereafter, the degree of migration of solder resist on the evaluation substrate was observed with a 100 × optical microscope.
〔Evaluation criteria〕
A: No short circuit. Furthermore, the occurrence of migration cannot be confirmed, and the insulation is excellent. ○: No short circuit. However, the occurrence of migration is confirmed slightly on copper. The occurrence of migration is confirmed slightly on copper. The occurrence of migration is also confirmed

<< Thermal shock resistance (crack resistance) >>
An insulating layer was formed on the line pattern of L / S = 75 μm / 125 μm using the photosensitive composition obtained above so that the film thickness on copper was 15 μm. Thereafter, 200 μm, 300 μm, and 400 μm round hole patterns were formed to obtain test plates. The obtained test plate is left in a liquid phase at −65 ° C. and 150 ° C. for 5 minutes each, and this is regarded as one cycle, and a 1,000 cycle test is performed, and a crack generated along the line pattern is observed. The occurrence of cracks was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: No occurrence of cracks ○: Generation of cracks is 5% or less for all round hole patterns △: Generation of cracks is 20% or less for all round hole patterns ×: Generation of cracks is all round holes 50% or less for the pattern

<< Resolution >>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, using a round hole pattern, a pattern forming apparatus is used to form a round hole having a width of 50 μm to 200 μm. ² was exposed.
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. did.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and there is no abnormality such as pattern residue, undercut, or peeling, and the smallest round hole pattern that can form a space The width was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution.
〔Evaluation criteria〕
A: A round hole with a diameter of 50 μm or less can be resolved, and the resolution is excellent. ○: A round hole with a diameter of 70 μm or less can be resolved, and the resolution is good. Δ: A round hole with a diameter of 100 μm or less. Can be resolved and resolution is slightly inferior ×: Round hole is not resolvable and resolution is inferior

(Examples 2 to 7)
In Example 1, while maintaining the total content of the acid-modified ethylenically unsaturated group-containing urethane resin and ethylenically unsaturated group-containing acrylic resin in the photosensitive composition, the type of resin, and the acid-modified ethylenically unsaturated group The ratio of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin in the total mass of the group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin is changed to the ratio shown in Table 1. In the same manner as in Example 1, a photosensitive composition, a photosensitive film, a photosensitive laminate, and the like were obtained.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, while maintaining the total content of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition, Example 1 except that the ratio of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin in the total mass with the ethylenically unsaturated group-containing acrylic resin was changed to the ratio shown in Table 1. In the same manner as above, a photosensitive composition, a photosensitive film, a photosensitive laminate, and the like were obtained.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In Example 3, except that the acid-modified ethylenically unsaturated group-containing urethane resin in the photosensitive composition was replaced with the urethane resin 1, the photosensitive composition, the photosensitive film, and the photosensitive property were obtained in the same manner as in Example 3. A laminate was obtained.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
In Example 3, except that the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition was replaced with the acrylic resin 1, the photosensitive composition, the photosensitive film, and the photosensitive laminate were obtained in the same manner as in Example 3. Etc.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

The mass% in Table 1 indicates the ratio of each resin in the total amount of urethane resin and acrylic resin in the photosensitive composition.

The photosensitive compositions of Examples 1 to 7 were excellent in insulation, thermal shock resistance, and resolution. The photosensitive compositions of Examples 1 to 7 are very excellent in thermal shock resistance compared to Comparative Example 1, and insulative, thermal shock resistance, and resolution compared to Comparative Examples 2 and 3. None of them were very good.
Moreover, the ratio of the acid-modified ethylenically unsaturated group-containing urethane resin in the total mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition is from 65% by mass to 65% by mass. In the case of 75% by mass (Examples 3 and 7), the insulation, thermal shock resistance, and resolution were all evaluated as “◎”, and were particularly excellent.

Since the photosensitive composition of this invention can obtain the high performance cured film excellent in insulation, thermal shock resistance, and resolution, it can be used suitably for a soldering resist.
Since the pattern forming method of the present invention uses the photosensitive composition, it is for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, a partition wall. It can be suitably used for the production of liquid crystal structural members such as holograms, micromachines, and proofs, and can be suitably used for the formation of permanent patterns on printed boards.

Claims (9)

  A photosensitive composition comprising an acid-modified ethylenically unsaturated group-containing urethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, and a photopolymerization initiator. The acid-modified ethylenically unsaturated group-containing urethane resin has a weight average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol / The photosensitive composition of Claim 1 which is g and contains at least 1 of the functional group represented by the following general formula (1) to (3) in a side chain.
However, in said general formula (1), R < ¹ > -R < ³ > represents either a hydrogen atom and a monovalent organic group each independently. X represents any of an oxygen atom, a sulfur atom, and —N (R ¹² ) —. R ¹² represents either a hydrogen atom or a monovalent organic group.
However, in said general formula (2), R < ⁴ > -R < ⁸ > represents either a hydrogen atom and a monovalent organic group each independently. Y represents an oxygen atom, a sulfur atom and -N ^{(R 12),} - represents either. R ¹² represents either a hydrogen atom or a monovalent organic group.
However, in said general formula (3), R < ⁹ > -R < ¹¹ > represents either a hydrogen atom and monovalent organic group each independently. Z represents an oxygen atom, a sulfur atom, -N (R 13) ^-, and represent any one of a phenylene group which may have a substituent. R ¹³ represents an alkyl group which may have a substituent.   The ethylenically unsaturated group-containing acrylic resin is epoxy-bonded to a part of the acid group of the copolymer obtained from a compound having (meth) acrylic acid ester and an ethylenically unsaturated group and having at least one acid group. The photosensitive composition according to claim 1, which is a modified copolymer to which a (meth) acrylate having a group is added.   Furthermore, the photosensitive composition in any one of Claim 1 to 3 containing a thermal crosslinking agent.   Furthermore, the photosensitive composition in any one of Claim 1 to 4 containing an inorganic filler.   The ratio of the acid-modified ethylenically unsaturated group-containing urethane resin in the total mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the ethylenically unsaturated group-containing acrylic resin is 55% by mass or more and 95% by mass or less. Item 6. The photosensitive composition according to any one of Items 1 to 5.   A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a substrate.   A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to claim 1. A printed circuit board comprising a permanent pattern formed by the method for forming a permanent pattern according to claim 8.